JPH04108523A - Manufacture of cyclodextrin membrane - Google Patents
Manufacture of cyclodextrin membraneInfo
- Publication number
- JPH04108523A JPH04108523A JP22746290A JP22746290A JPH04108523A JP H04108523 A JPH04108523 A JP H04108523A JP 22746290 A JP22746290 A JP 22746290A JP 22746290 A JP22746290 A JP 22746290A JP H04108523 A JPH04108523 A JP H04108523A
- Authority
- JP
- Japan
- Prior art keywords
- cyclodextrin
- membrane
- plasticizer
- derivative
- support
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 45
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000003892 spreading Methods 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 239000011521 glass Substances 0.000 abstract description 7
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 abstract description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 2
- 229920006362 Teflon® Polymers 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000001116 FEMA 4028 Substances 0.000 description 5
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 5
- 229960004853 betadex Drugs 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- LPKZGAGGBDTXOZ-UHFFFAOYSA-N [1-nitro-8-(8-nitro-8-phenyloctoxy)octyl]benzene Chemical compound C=1C=CC=CC=1C([N+](=O)[O-])CCCCCCCOCCCCCCCC([N+]([O-])=O)C1=CC=CC=C1 LPKZGAGGBDTXOZ-UHFFFAOYSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GRFFKYTUNTWAGG-UHFFFAOYSA-N chloroethene;prop-2-enenitrile Chemical compound ClC=C.C=CC#N GRFFKYTUNTWAGG-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 1
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はシクロデキストリン膜の製造方法に関し、更に
詳しくは機能性の分離膜や透過膜などに用いられるシク
ロデキストリン膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a cyclodextrin membrane, and more particularly to a method for producing a cyclodextrin membrane used for functional separation membranes, permeation membranes, and the like.
［従来の技術］
シクロデキストリンは水溶液中で種々のゲスト化合物と
構造特異的な包接化合物を形成する。したがって、シク
ロデキストリンを含む固体膜には、特異的な分離能と透
過能などが期待され、またシクロデキストリンが高分子
に担持されることにより単体として成し得なかった種々
の物性を期待することができ、利用面も広がるため、シ
クロデキストリンを含む膜を自由に作成しうる方法が望
まれていた。[Prior Art] Cyclodextrins form structure-specific inclusion compounds with various guest compounds in aqueous solutions. Therefore, solid membranes containing cyclodextrin are expected to have specific separation ability and permeability, and by supporting cyclodextrin on polymers, various physical properties that could not be achieved as a single substance are expected. Since this method can be used to expand the range of applications, there has been a desire for a method that can freely create membranes containing cyclodextrin.
このようなシクロデキストリン膜の作成に関して、例え
ば特開昭６０−２３２２１０号公報には、シクロデキス
トリンの包接化合物の結晶とイソシアネート基を有する
化合物からなる高分子を市販の限外濾過膜上にキャスト
する方法が開示されており、また、特開昭６２−２５８
７０２号公報にはシクロデキストリンと各種モノマーを
反応させた一後アクリロニトリル誘導体と共重合して得
られた高分子を公知の方法を用いて製膜する方法が開示
されている。Regarding the preparation of such a cyclodextrin membrane, for example, Japanese Patent Application Laid-Open No. 60-232210 discloses that a polymer consisting of crystals of a cyclodextrin clathrate compound and a compound having an isocyanate group is cast onto a commercially available ultrafiltration membrane. A method for
Publication No. 702 discloses a method of forming a film using a known method from a polymer obtained by reacting cyclodextrin with various monomers and then copolymerizing it with an acrylonitrile derivative.
［発明が解決しようとする課題］
しかしながら、前記特開昭６０−２３２２１０号開示の
方法はシクロデキストリン膜を高分子自体の膜として使
用しうるち、のではなく、また、特開昭６２−２５８７
０２号開示の方法は、得られる高分子膜中のシクロデキ
ストリンの導入率が低く十分なものではなかった。[Problems to be Solved by the Invention] However, the method disclosed in JP-A No. 60-232210 uses a cyclodextrin membrane as a membrane of the polymer itself;
The method disclosed in No. 02 was not sufficient because the rate of cyclodextrin introduction into the resulting polymer membrane was low.
従って、本発明の目的は、シクロデキストリンを膜内に
保持し、単体かつ強度の高い膜として使用しつるシクロ
デキストリン膜の製造方法を提供することにある。Accordingly, an object of the present invention is to provide a method for producing a cyclodextrin membrane in which cyclodextrin is retained within the membrane and used as a single, strong membrane.
［課題を解決するための手段］
本発明者等は前記課題に鑑みて鋭意研究の結果、本発明
の上記目的は、シクロデキストリン又はその誘導体を製
膜機能を有する高分子化合物及び可塑剤と共に溶媒に溶
解して得られる溶液を支持体上に展延した後乾燥するこ
とを特徴とするシクロデキストリン膜の製造方法により
達成されることを見出した。[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have conducted intensive research and found that the above-mentioned object of the present invention is to combine cyclodextrin or its derivatives with a polymer compound having a film-forming function and a plasticizer together with a solvent. It has been found that this can be achieved by a method for producing a cyclodextrin membrane, which is characterized by spreading a solution obtained by dissolving it on a support and then drying it.
以下に本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明において製膜機能を有する高分子化合物としては
、ポリビニルアルコール、ポリ塩化ビニル、ポリ塩化ビ
ニリデン、ポリアクリロニトリル、ポリスチレン、ポリ
エチレン、ポリプロピレン、ポリメタクリル酸エステル
（例えば、ポリメタクリル酸メチル）、ポリアクリル酸
エステル（例えばポリアクリル酸メチル）、ポリカーボ
ネート、ポリブタジェン、ポリ酢酸ビニル、ポリスルホ
ン（例えば、ポリエーテルスルホン、ポリフェニルスル
ホン）、ポリアミド（例えば、ポリエーテルアミド）、
ポリイミド、ポリＮ−ビニルピロリドン、ポリエチレン
テレフタレート、エチレン−酢酸ビニル共重合体、ある
いはそのケン化物であるエチレン−ビニルアルコール共
重合体、アクリロニトリル−メタクリルスルホン酸ナト
リウム共重合体、アクリロニトリル−塩化ビニル（又は
塩化ビニリデン）共重合体、ポリエーテルカーボネート
、ブタジェン−アクリロニトリル共重合体、エチレン−
無水マレイン酸共重合体、メタクリル酸（又はアクリル
酸）エステル（例えばメタクリル酸（又はアクリル酸）
メチル）−Ｎ−ビニルピロリドン共重合体、スチレン−
ブタジェン（スチレンをクロロメチル化又はアミノ化し
たものも含む）共重合体、スチレン−ジビニルベンゼン
共重合体、スチレン−ジビニルベンゼン−塩化ビニル共
重合体、セルロース系化合物（例えばニトロセルロース
、エチルセルロース、アセチルセルロース）等又はこれ
らの組合わせが用いられる。In the present invention, examples of polymer compounds having a film-forming function include polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polystyrene, polyethylene, polypropylene, polymethacrylic acid ester (for example, polymethyl methacrylate), polyacrylic acid Esters (e.g. polymethyl acrylate), polycarbonates, polybutadiene, polyvinyl acetate, polysulfones (e.g. polyethersulfone, polyphenylsulfone), polyamides (e.g. polyetheramide),
Polyimide, polyN-vinylpyrrolidone, polyethylene terephthalate, ethylene-vinyl acetate copolymer or its saponified ethylene-vinyl alcohol copolymer, acrylonitrile-sodium methacrylsulfonate copolymer, acrylonitrile-vinyl chloride (or chloride) vinylidene) copolymer, polyether carbonate, butadiene-acrylonitrile copolymer, ethylene-
Maleic anhydride copolymer, methacrylic acid (or acrylic acid) ester (e.g. methacrylic acid (or acrylic acid)
methyl)-N-vinylpyrrolidone copolymer, styrene-
Butadiene (including chloromethylated or aminated styrene) copolymers, styrene-divinylbenzene copolymers, styrene-divinylbenzene-vinyl chloride copolymers, cellulose compounds (e.g. nitrocellulose, ethylcellulose, acetylcellulose) ) etc. or a combination thereof may be used.
また、本発明において、シクロデキストリン又はその誘
導体、及び上記高分子化合物と共に用いられる可塑剤と
しては有機酸エステル型可塑剤とリン酸エステル型可塑
剤が挙げられるが、前記高分子化合物、シクロデキスト
リン等の相溶性の点から有機酸エステル型可塑剤が好ま
しく用いられる。Furthermore, in the present invention, examples of the plasticizer used together with cyclodextrin or its derivative and the above-mentioned polymer compound include organic acid ester type plasticizers and phosphate ester type plasticizers. Organic acid ester type plasticizers are preferably used from the viewpoint of compatibility.
このような可塑剤としては具体的には、ジオクチルフタ
レート（ＤＯＰ） 、ビス−２−エチルへキシルセバケ
ート（ＤＯ８）、ニトロフェニルオクチルエーテル（Ｎ
ＰＯＥ） 、ニドセフェニルフェニルエーテル（ＮＰＰ
Ｅ） 、）リス−２−エチルへキシルフタレート（ＴＥ
ＨＰ） 、フルオロフェニル壷二トロフェニルエーテ４
（ＦＰＮＰＥ）等が挙げられる。Specific examples of such plasticizers include dioctyl phthalate (DOP), bis-2-ethylhexyl sebacate (DO8), and nitrophenyl octyl ether (N
POE), nidosephenyl phenyl ether (NPP
E) ,) Lis-2-ethylhexyl phthalate (TE
HP), Fluorophenyl Pot Nitrophenyl Ethe 4
(FPNPE), etc.
本発明においては、前記高分子化合物と可塑剤をシクロ
デキストリン又はその誘導体と共に溶媒に溶解し、支持
体上に塗設するものであるが、この際、用いられる溶媒
としては、水又は有機溶媒であり、有機溶媒としては特
に、テトラヒドロフラン（ＴＨＦ） 、塩化メチレン、
アセトン、ジメチルホルムアミド（ＤＭＦ） 、ジメチ
ルスルホキシド（ＤＭＳＯ） 、等が好ましく用いられ
る。In the present invention, the above-mentioned polymer compound and plasticizer are dissolved in a solvent together with cyclodextrin or its derivative, and the solution is coated on a support. In this case, the solvent used is water or an organic solvent. Examples of organic solvents include tetrahydrofuran (THF), methylene chloride,
Acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc. are preferably used.
本発明においては、前記製膜機能を有する高分子化合物
１モルに対し、可塑剤を５〜５０モル、好ましくは１０
〜２０モル、シクロデキストリン又はその誘導体を１〜
２０モル、好ましくは１〜５モルに相当する配合比にて
、水又は前記有機溶媒に溶解し、得られる溶液をガラス
板、テフロン板、金属板等の支持体上に展延し、乾燥す
ることによりシクロデキストリン膜を得ることができる
。In the present invention, the amount of plasticizer is 5 to 50 mol, preferably 10 mol to 1 mol of the polymer compound having a film forming function.
~20 moles, 1~20 moles of cyclodextrin or its derivative
Dissolve in water or the organic solvent at a blending ratio equivalent to 20 mol, preferably 1 to 5 mol, and spread the resulting solution on a support such as a glass plate, Teflon plate, metal plate, etc., and dry. A cyclodextrin membrane can be obtained by this.
本発明にお′いてシクロデキストリンの誘導体を形成す
るシクロデキストリンとしては、例えばα−シクロデキ
ストリン、β−シクロデキストリン及びγ−シクロデキ
ストリンが挙げられる。また、本発明に用いられるシク
ロデキストリンの誘導体としては、例えば、メチル化β
−シクロデキストリン、アセチル化β−シクロデキスト
リン等が挙げられる。Examples of the cyclodextrin forming the cyclodextrin derivative in the present invention include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Further, as the cyclodextrin derivatives used in the present invention, for example, methylated β
-cyclodextrin, acetylated β-cyclodextrin, and the like.
本発明においてはシクロデキストリンとブレンドさせる
高分子化合物が製膜能を有しているため、他の支持膜の
助けを得ることなくシクロデキストリン膜を製造するこ
とができ、また、膜強度についても可塑剤を添加するこ
とにより高分子化合物とシクロデキストリン誘導体が分
離することなく強化することができ、連続操作性に耐え
うるシクロデキストリン膜を製造することができる。In the present invention, since the polymer compound blended with cyclodextrin has film-forming ability, a cyclodextrin film can be produced without the aid of other supporting films, and the film strength is also reduced by plasticity. By adding the agent, the polymer compound and the cyclodextrin derivative can be strengthened without separating, and a cyclodextrin membrane that can withstand continuous operation can be produced.
更に、膜の劣化が著しい条件下で使用する場合にも、シ
クロデキストリンの水酸残基を架橋させることにより膜
を不溶化することができる。Furthermore, even when the membrane is used under conditions where the membrane deteriorates significantly, the membrane can be made insolubilized by crosslinking the hydroxyl residues of cyclodextrin.
本発明のシクロデキストリン膜は、例えば光学異性体な
どの分離膜、特定物質の濃縮等を行なう透過膜などとし
て利用することができる。The cyclodextrin membrane of the present invention can be used, for example, as a separation membrane for optical isomers, a permeable membrane for concentrating specific substances, and the like.
以下に、本発明の具体的実施例を挙げる。Specific examples of the present invention are listed below.
［実施例］
実施例１
ポリ塩化ビニル（分子量：約１万）５ｇ１可塑剤Ｎ Ｐ
ＯＥ ２．５ｇ 、及びメチル化β−シクロデキスト
リン２０ｇをＴＨＦ （テトラヒドロフラン）１００ｄ
に溶・解しよく撹拌する。その後ＴＨＦを減圧下、溶解
物が析出する直前まで濃縮し、得られた溶液をガラス板
などの支持体の上に展延した後、溶媒（ＴＨＦ）を蒸発
させ、シクロデキストリン膜を作製した。[Example] Example 1 Polyvinyl chloride (molecular weight: approximately 10,000) 5g 1 plasticizer N P
2.5 g of OE and 20 g of methylated β-cyclodextrin were mixed with 100 d of THF (tetrahydrofuran).
Dissolve and stir well. Thereafter, THF was concentrated under reduced pressure until just before the dissolved substance precipitated, and the resulting solution was spread on a support such as a glass plate, and then the solvent (THF) was evaporated to prepare a cyclodextrin membrane.
実施例２
ポリメタクリル酸メチル（分子量：約１万）５ｇ、可塑
剤Ｄ ＯＰ １．５ｇ及びアセチル化β−シクロデキス
トリン２．５ｇをＴ ＨＦ １００ｖｆｉに溶解しよく
撹拌する。その後ＴＨＦを減圧下、溶解物が析出する直
前まで濃縮し得られた粘稠液体をガラス板などの支持体
の上に展延した後、溶媒を完全に蒸発させ、シクロデキ
ストリン膜を作製した。Example 2 5 g of polymethyl methacrylate (molecular weight: about 10,000), 1.5 g of plasticizer D OP and 2.5 g of acetylated β-cyclodextrin are dissolved in 100 vfi of T HF and stirred well. Thereafter, THF was concentrated under reduced pressure until just before the melt was precipitated, and the resulting viscous liquid was spread on a support such as a glass plate, and the solvent was completely evaporated to prepare a cyclodextrin membrane.
実施例３
ポリＮ−ビニルピロリドン（分子量：約５万）１０ｇ１
可塑剤ＤＯＰ２．０ｇ及びアセチル化β−シクロデキス
トリン２．５ｇを塩化メチレン５０ｄに溶解し、よく撹
拌する。その後塩化メチレンを減圧下溶解物が析出する
直前まで濃縮し、得られた溶液をガラス板などの支持体
の上に展延した後、溶媒を蒸発させ、シクロデキストリ
ン膜を作製した。Example 3 Poly N-vinylpyrrolidone (molecular weight: approximately 50,000) 10g1
2.0 g of plasticizer DOP and 2.5 g of acetylated β-cyclodextrin are dissolved in 50 d of methylene chloride and stirred well. Thereafter, methylene chloride was concentrated under reduced pressure until just before the solution was precipitated, and the resulting solution was spread on a support such as a glass plate, and the solvent was evaporated to prepare a cyclodextrin membrane.
実施例４
ポリエチレン−無水マレイン酸共重合体（分子量：約１
５万）５ｇ１可塑剤Ｎ Ｐ ＯＥ １．５ｇ及びメチル
化β−シクロデキストリン２．０ｇをアセトン５０ｕＪ
２に溶解し、よく撹拌する。その後アセトンを減圧下、
溶解物が析出する直前まで濃縮し、得られた溶液をガラ
ス板などの支持体の上に展延した後、溶媒を蒸発させ、
シクロデキストリン膜を作製した。Example 4 Polyethylene-maleic anhydride copolymer (molecular weight: about 1
50,000) 5g1 plasticizer N POE 1.5g and methylated β-cyclodextrin 2.0g acetone 50uJ
2 and stir well. Then add acetone under reduced pressure.
Concentrate until just before the dissolved substance precipitates, spread the resulting solution on a support such as a glass plate, and then evaporate the solvent.
A cyclodextrin membrane was prepared.
実施例５
ポリエチレン−ビニルアルコール共重合体（酢酸ビニル
をケン化したもの、分子量：約１万）５ｇ１可塑剤Ｄ
ＯＳ ２．０ｇ及びβ−シクロデキストリン２．Ｏｇを
Ｄ Ｍ Ｆ １００ｄに溶解する。その後ＤＭＦを減圧
下４０〜５０℃で溶解物が析出する直前まで濃縮し、得
られた粘稠液体をガラス板などの支持体の上に展延した
後４０〜５０℃に加熱し、ある程度蒸発した時点で水中
に入れ、膜を剥し、シクロデキストリン膜を得た。Example 5 Polyethylene-vinyl alcohol copolymer (saponified vinyl acetate, molecular weight: approximately 10,000) 5g 1 Plasticizer D
2.0 g of OS and β-cyclodextrin 2. Dissolve Og in DMF 100d. Thereafter, DMF is concentrated under reduced pressure at 40 to 50°C until just before the melt precipitates, and the resulting viscous liquid is spread on a support such as a glass plate, heated to 40 to 50°C, and evaporated to some extent. At that point, it was placed in water and the membrane was peeled off to obtain a cyclodextrin membrane.
［発明の効果］
以上詳細に説明したように、本発明の製造方法により、
シクロデキストリンを膜内に保持することができ、単体
かつ強度の高い膜として使用しうるシクロデキストリン
膜を提供することができる。[Effects of the Invention] As explained in detail above, the manufacturing method of the present invention provides
It is possible to provide a cyclodextrin membrane that can retain cyclodextrin within the membrane and can be used as a single, strong membrane.
Claims (1)
高分子化合物及び可塑剤と共に溶媒に溶解して得られる
溶液を支持体上に展延した後乾燥することを特徴とする
シクロデキストリン膜の製造方法。1. A method for producing a cyclodextrin membrane, which comprises spreading a solution obtained by dissolving cyclodextrin or a derivative thereof in a solvent together with a polymer compound having a membrane-forming function and a plasticizer on a support, and then drying the resulting solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22746290A JPH04108523A (en) | 1990-08-29 | 1990-08-29 | Manufacture of cyclodextrin membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22746290A JPH04108523A (en) | 1990-08-29 | 1990-08-29 | Manufacture of cyclodextrin membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04108523A true JPH04108523A (en) | 1992-04-09 |
Family
ID=16861256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22746290A Pending JPH04108523A (en) | 1990-08-29 | 1990-08-29 | Manufacture of cyclodextrin membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04108523A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492947A (en) * | 1994-06-23 | 1996-02-20 | Aspen Research Corporation | Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative |
| US6851462B2 (en) | 2001-10-30 | 2005-02-08 | The Goodyear Tire & Rubber Company | Rubber compositions containing a cyclodextrin compound |
| JP2019195767A (en) * | 2018-05-09 | 2019-11-14 | 株式会社都ローラー工業 | Fresh water generator |
-
1990
- 1990-08-29 JP JP22746290A patent/JPH04108523A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492947A (en) * | 1994-06-23 | 1996-02-20 | Aspen Research Corporation | Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative |
| US5505969A (en) * | 1994-06-23 | 1996-04-09 | Aspen Research Corporation | Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative |
| US5603974A (en) * | 1994-06-23 | 1997-02-18 | Aspen Research Corporation | Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative |
| US6851462B2 (en) | 2001-10-30 | 2005-02-08 | The Goodyear Tire & Rubber Company | Rubber compositions containing a cyclodextrin compound |
| JP2019195767A (en) * | 2018-05-09 | 2019-11-14 | 株式会社都ローラー工業 | Fresh water generator |
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